CN116761577A

CN116761577A - Glass reinforced container, method for producing pharmaceutical container, and method for producing glass reinforced container

Info

Publication number: CN116761577A
Application number: CN202180089777.8A
Authority: CN
Inventors: 寺田达也; 西舞; 细田朋也
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2021-01-08
Filing date: 2021-12-28
Publication date: 2023-09-15
Also published as: JPWO2022149552A1; KR20230129473A; EP4276081A1; WO2022149552A1; US20230339805A1

Abstract

A reinforced glass container having impact resistance and usable even in connection with a treatment involving high-temperature exposure or ultraviolet irradiation is provided. The glass reinforced container of the present invention comprises a glass container and a polymer layer having a thickness of more than 1 [ mu ] m provided on the outer surface of the glass container, wherein the polymer layer comprises a tetrafluoroethylene polymer having a carbonyl group or hydroxyl group and having a melting temperature of more than 260 ℃.

Description

Glass reinforced container, method for producing pharmaceutical container, and method for producing glass reinforced container

Technical Field

The present invention relates to a glass reinforced container, a method for producing a pharmaceutical container, and a method for producing a glass reinforced container.

Background

The glass container has excellent chemical resistance, air tightness, transparency, and the like. Therefore, glass containers are used as containers for containing pharmaceuticals, and are widely used as ampoules and vials. However, glass is easily broken by impact, and glass containers are easily broken by transportation or contact when filled with contents. Therefore, a technique of providing a polymer layer on the outer surface of a glass container to improve the impact resistance of the glass container is employed, but it is not easy to firmly bond the glass and the polymer layer.

Patent document 1 proposes a glass container in which a base layer is provided on an outer surface thereof using a silane coupling agent, and a polymer layer is further provided on the base layer.

Patent document 2 proposes a glass container in which an undercoat layer made of a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP) is provided on the outer surface, and a top coat layer made of a fluoroolefin polymer is further provided on the undercoat layer.

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2015-515433

Patent document 2: japanese patent laid-open No. 9-206606

Disclosure of Invention

Technical problem to be solved by the invention

In recent years, there are increasing cases where high hygiene management is required for glass containers, and for example, sterilization treatment by exposure to high temperature or ultraviolet light for a long period of time is often performed on glass containers used for storing pharmaceuticals. However, the present inventors have found that the glass containers described in patent documents 1 and 2 cannot be used as glass containers satisfying such requirements.

Specifically, the glass container described in patent document 1 has a problem that the original impact resistance is still insufficient. Further, there is a problem that the impact resistance is lowered and the polymer layer itself is easily peeled off, as well as the base layer or the polymer layer is deteriorated by high temperature exposure or ultraviolet irradiation.

The glass container described in patent document 2 has a problem that the coating layer is melted when exposed to high temperature and the sterilization treatment itself cannot be sufficiently performed because the adhesion between the outer surface thereof and the coating layer is still insufficient.

As a result of intensive studies, the present inventors have found that, when a predetermined tetrafluoroethylene polymer layer is provided on the outer surface of a glass container, a glass reinforced container having impact resistance and usable even with a treatment involving high temperature exposure or ultraviolet irradiation can be obtained.

The present invention provides a glass reinforced container and a method for producing the same, and a method for producing a pharmaceutical container using the glass reinforced container.

Means for solving the technical problems

The present invention has the following configurations.

[1] A glass reinforced container comprising a glass container and a polymer layer having a thickness of more than 1 [ mu ] m provided on the outer surface of the glass container, wherein the polymer layer comprises a tetrafluoroethylene polymer having a carbonyl group or hydroxyl group and having a melting temperature of more than 260 ℃.

[2] The glass reinforced container according to [1], wherein the compressive strength of the tetrafluoroethylene polymer exceeds 12MPa.

[3]Such as [1]]Or [2]]The glass reinforced container, wherein the tetrafluoroethylene polymer is 1X 10 ⁶ Tetrafluoroethylene polymer having 10 to 5000 carbonyl groups in its main chain carbon number.

[4] The glass reinforced container according to any one of [1] to [3], wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer containing a perfluoro (alkyl vinyl ether) -based unit.

[5] The glass-made reinforced container according to any one of [1] to [4], wherein the glass container is composed of borosilicate glass or alkali-containing aluminosilicate glass.

[6] The glass reinforced container according to any one of [1] to [5], wherein the glass container has a thickness of 2mm or less.

[7] The glass reinforced container as recited in any one of [1] to [6], wherein the polymer layer further comprises polytetrafluoroethylene.

[8] The glass reinforced container as described in any one of [1] to [7], wherein the thickness of the polymer layer exceeds 20. Mu.m.

[9] The glass reinforced container as described in any one of [1] to [8], wherein the thickness of the polymer layer is less than 40. Mu.m.

[10] The glass reinforced container according to any one of [1] to [9], wherein the glass container is a vial, ampoule, bottle or cartridge.

[11] The glass reinforced container according to any one of [1] to [10], which is used in a pharmaceutical product.

[12] A method for producing a pharmaceutical product container, wherein the glass-made reinforced container of any one of [1] to [11] is exposed to ultraviolet light or an atmosphere having a temperature of 200 ℃ or higher and a melting temperature of the tetrafluoroethylene polymer or lower, whereby the glass-made reinforced container is obtained after the sterilization treatment, and the glass-made reinforced container is filled with a pharmaceutical product and sealed, whereby the pharmaceutical product container in which the pharmaceutical product is contained in the glass-made reinforced container is obtained.

[13] A method for producing a glass reinforced container, wherein a liquid composition comprising particles of a tetrafluoroethylene polymer having a carbonyl group or a hydroxyl group and having a melting temperature of more than 260 ℃ is applied to an outer surface of a glass container and heated, and a polymer layer having a thickness of more than 1 [ mu ] m comprising the tetrafluoroethylene polymer is formed on the outer surface of the glass container, thereby obtaining a glass reinforced container comprising the glass container and the polymer layer provided on the outer surface of the glass container.

[14] The production method according to [13], wherein the liquid composition is applied to the outer side surface of the glass container by a dip coating method.

[15] The method according to [13] or [14], wherein the viscosity of the liquid composition is 1000 mPas or less.

Effects of the invention

According to the present invention, a glass reinforced container excellent in impact resistance, heat resistance and UV resistance can be obtained, and a container for pharmaceutical products and the like, which is required to be highly hygienic and managed, can be efficiently produced.

Detailed Description

The following terms have the following meanings.

The "average particle diameter (D50)" is a cumulative 50% diameter based on the volume of the object (particles or filler) obtained by the laser diffraction/scattering method. That is, the particle size distribution was measured by a laser diffraction/scattering method, and a cumulative curve was obtained with the total volume of the particle clusters being 100%, and the particle diameter at the point on the cumulative curve where the cumulative volume reached 50%.

The "melting temperature" is a temperature corresponding to the maximum value of the melting peak of the polymer measured by the Differential Scanning Calorimeter (DSC) method.

"glass transition temperature (Tg)" is a value measured by analyzing a polymer by dynamic viscoelasticity measurement (DMA).

The "viscosity" means a viscosity obtained by measuring a liquid composition at 25℃under a rotation speed of 60rpm using a type B viscometer. The measurement was repeated 3 times, and the average of the 3 measured values was taken.

"thixotropic ratio" means the viscosity η of the liquid composition measured at a rotational speed of 30rpm ₁ Divided by the viscosity eta of the liquid composition measured at a rotation speed of 60rpm ₂ And the calculated value. The measurement of each viscosity was repeated 3 times, and the average of the 3 measured values was taken.

The "specific surface area" is a value calculated by measuring particles or fillers by a BET multipoint method by gas adsorption (constant volume method), and is obtained by using NOVA 4200e (manufactured by Kang Da instruments (Quantachrome Instruments)).

"Unit" in a polymer refers to an atomic group formed directly from 1 molecule of monomer by polymerization, and a portion of the atomic group is converted to an atomic group of other structure by treatment of the resulting polymer. Hereinafter, the unit based on the monomer a is also simply referred to as "monomer a unit".

The glass reinforced container (hereinafter also referred to as "present container") of the present invention comprises a glass container and a polymer layer (hereinafter also referred to as "F layer") having a thickness exceeding 1 μm provided on the outer surface of the glass container. The F layer contains a tetrafluoroethylene polymer having a carboxyl group or hydroxyl group (hereinafter also referred to as "F polymer") with a melting temperature exceeding 260 ℃.

The container is excellent in impact resistance, heat resistance and UV resistance. The reason for this is not necessarily clear, but is considered as follows.

The F polymer in the container is a fluoropolymer with heat resistance and ultraviolet resistance and with a melting temperature exceeding 260 ℃. Thus, the shape retention of the F layer in a high temperature atmosphere or exposure to ultraviolet rays is enhanced.

In addition, the F polymer having a melting temperature has a certain plasticity and elasticity, and is said to be rich in flexibility. Therefore, by forming the F layer with a predetermined thickness or more, the impact resistance of the present container can be improved.

In addition, the F polymer has carbonyl-containing groups or hydroxyl-containing groups that interact with polar functional groups such as silanol groups present on the outside surface of the glass container, thus allowing the outside surface to firmly adhere to the F polymer.

By the synergistic effect of these effects, it is considered that a glass reinforced container excellent in impact resistance and usable even with a treatment accompanied by high-temperature exposure or ultraviolet irradiation is obtained.

The F layer of the present container is preferably disposed directly on the outside surface of the glass container. In other words, the present container has a glass container and an F layer, preferably a glass container containing an F polymer, disposed directly on the outer side surface of the glass container. In this case, the above mechanism of action becomes remarkable, and the impact resistance, heat resistance and UV resistance of the present container tend to be further improved.

The F polymer is a heat-fusible polymer containing a unit (TFE unit) based on tetrafluoroethylene (hereinafter also referred to as "TFE"). Therefore, the F layer is excellent in flexibility and adhesion to the outer surface of the glass container. The hot melt property means a polymer exhibiting melt fluidity, and the polymer has a melt flow rate of 0.1 to 1000g/10 minutes at a temperature 20 ℃ or higher than the melting temperature of the polymer under a load of 49N.

The melting temperature of the F polymer exceeds 260℃and is preferably 280 to 320 ℃. In this case, the heat resistance of the F layer tends to be good.

The fluorine atom content in the F polymer is preferably 70 mass% or more, more preferably 74 to 76 mass%. In this case, the UV resistance durability of the F layer is more easily improved.

The glass transition temperature of the F polymer is preferably 75 to 125℃and more preferably 80 to 100 ℃.

Examples of the F polymer include: a polymer containing TFE units and ethylene units, a polymer containing TFE units and propylene units, a polymer containing TFE units and units based on perfluoro (alkyl vinyl ether) (hereinafter also referred to as "PAVE") units (PAVE units) (PFA), a polymer containing TFE units and units based on fluoroalkyl ethylene (PFA), preferably PFA. If PFA is used as the F polymer, the impact resistance of the container is easily improved. The above polymers may also contain units based on other comonomers.

As PAVE, CF is preferred ₂ ＝CFOCF ₃ 、CF ₂ ＝CFOCF ₂ CF ₃ And CF (compact F) ₂ ＝

CFOCF ₂ CF ₂ CF ₃ (PPVE), more preferably PPVE.

The F polymer has a carbonyl-containing group or a hydroxyl-containing group (hereinafter also referred to collectively as "oxygen-containing polar groups"). Since the F polymer contains the oxygen-containing polar group, the F layer adheres firmly to the outer surface of the glass container, and also exhibits excellent high-temperature adhesion.

The oxygen-containing polar groups may be contained in units in the F polymer or may be contained in terminal groups of the F polymer backbone. The latter form may be exemplified by an F polymer having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like, or an F polymer having an oxygen-containing polar group obtained by subjecting an F polymer to plasma treatment or ionizing radiation treatment.

The F polymer preferably has carbonyl-containing groups. In this case, the F layer has excellent adhesion and adhesiveness to the outer surface of the glass container.

As the hydroxyl group-containing group, an alcoholic hydroxyl group-containing group is preferable, and-CF is more preferable ₂ CH ₂ OH、-C(CF ₃ ) ₂ OH and 1, 2-ethanediol (-CH (OH) CH) ₂ OH)。

The carbonyl-containing group is a carbonyl (> C (O)) containing group, and as the carbonyl-containing group, carboxyl, alkoxycarbonyl, amide, isocyanate, and carbamate (-OC (O) NH) groups are preferable ₂ ) Anhydride residue (-CO (O) OC (O) -), imide residue (-C (O) NHC (O) -, etc.), and carbonate group (-OC (O) O-), more preferably anhydride residue.

In the case where the F polymer has carbonyl-containing groups, the number of carbonyl-containing groups in the F polymer is 1X 10 ⁶ The number of main chain carbons is preferably 10 to 5000, more preferably 50 to 4000, and still more preferably 100 to 2000. In this case, the adhesion of the F layer to the outer surface of the glass container is more easily improved. The number of carbonyl groups in the F polymer can be determined according to the composition of the polymer or the method described in International publication No. 2020/145133.

The F polymer is preferably a polymer having an oxygen-containing polar group and containing TFE units and PAVE units, more preferably a polymer having TFE units, PAVE units and units based on a monomer having an oxygen-containing polar group, and even more preferably a polymer containing these units in the order of 90 to 99 mol%, 0.5 to 9.97 mol%, and 0.01 to 3 mol% relative to the total units.

Further, as the monomer having an oxygen-containing polar group, itaconic anhydride, citraconic anhydride or 5-norbornene-2, 3-dicarboxylic anhydride (hereinafter also referred to as "NAH") is preferable.

Specific examples of the polymer include those described in International publication No. 2018/16644.

The F polymer is easily more densely and homogeneously distributed in the F layer. Further, the fine spherulites are easily formed in the F layer, and adhesion with other components is easily improved. As a result, the F layer having high adhesion to the outer surface of the glass container can be obtained more easily.

The compressive strength of the F polymer is a value determined according to ASTM-D695. Specifically, the compressive strength of the F polymer is preferably more than 12MPa, more preferably 15MPa or more. The compressive strength of the F polymer is preferably 40MPa or less. In this case, the high-temperature adhesiveness of the F layer is easily improved.

The transmittance of the F layer at a wavelength of 255 to 355nm is preferably 80% or more. In this case, the visibility of the content (for example, medicine) stored in the container is improved when viewed from the outside. In the present container having excellent recognition, the F layer is preferably composed mainly of an F polymer, and preferably substantially only of the F polymer. The F layer being substantially composed of only the F polymer means that the content of the F polymer in the F layer is 90 mass% or more.

The peel strength of the glass container from the F layer is preferably 5N/cm or more, more preferably 8N/cm or more. Thereby preventing the F layer from being easily peeled from the glass container.

The thickness of the F layer exceeds 1. Mu.m, preferably exceeds 20. Mu.m. In addition, the thickness of the F layer is preferably less than 40. Mu.m. The impact resistance, heat resistance and UV resistance of the present container provided with the F layer having such a thickness are more easily improved.

The void ratio of the F layer is preferably 5% or less, more preferably 4% or less. The void ratio of the F layer is preferably 0.01% or more, more preferably 0.1% or more.

The void ratio of the F layer is a ratio (%) obtained by determining a void portion of the F layer by image processing from an SEM photograph of a cross section of the F layer observed by a Scanning Electron Microscope (SEM) and dividing the area occupied by the void portion by the area of the F layer.

The area occupied by the void portion is obtained by approximating the void portion to a circular shape.

The F layer may contain a resin material other than the F polymer described later in the method for producing a container, and preferably also Polytetrafluoroethylene (PTFE). The present container in which the F layer contains the F polymer and PTFE has excellent low friction characteristics, and not only can prevent the adhesion of foreign matter, but also can contribute to improvement of handling properties such as transportation. In addition, the resistance (heat resistance and UV resistance) of the F layer to the sterilization treatment is more easily improved.

In the case where the F layer contains the F polymer and PTFE, the content of the F polymer and the content of PTFE in the F layer are each independently preferably 10 to 90 mass%. The mass ratio of the PTFE content to the F polymer content in the F layer is preferably 1 or more. The mass ratio is preferably 20 or less, more preferably 10 or less.

PTFE is a non-heat-fusible tetrafluoroethylene polymer having TFE units as main units, and may be exemplified by a homopolymer of TFE and a copolymer of TFE with a very small amount of a comonomer (HFP, PAVE, FAE, etc.). .

The use of the glass container is not particularly limited, and the glass container can be suitably used as a container for storing and preserving a pharmaceutical product. Such a container may be a vial, ampoule, bottle, cartridge, syringe (outer tube and plunger), beaker, culture dish, or the like, and preferably a vial, ampoule, bottle, or cartridge.

The glass container may be chemically strengthened prior to formation of the F layer, and thus mechanical durability of the glass container may be improved by this treatment. Therefore, the glass container may be ion exchange strengthened prior to formation of the F layer. The glass in this case is also referred to as "ion-exchanged glass". As a specific example of ion exchange strengthening of a glass container, there can be mentioned a method in which a glass container is subjected to 100% KNO ₃ Immersing in a molten salt bath at 450 ℃ for about 8 hours. Furthermore, it is possible to provide a device for the treatment of a disease. The glass container may be strengthened by other strengthening methods such as heat strengthening and flame grinding.

The glass container may be formed of a glass composition containing ion-exchangeable glass and ion-non-exchangeable glass, or may be formed of a type 1B glass composition such as schottky type 1B aluminosilicate glass.

The glass container is preferably made of glass conforming to the standards related to medical glass described by regulatory authorities such as United states Pharmacopeia, european Pharmacopeia and Japanese Pharmacopeia based on hydrolysis resistance.

As the glass constituting the glass container, soda lime glass, alkali-containing aluminosilicate glass or borosilicate glass is preferable, and alkali-containing aluminosilicate glass or borosilicate glass is more preferable. These glasses are preferable because they have a low linear expansion coefficient, a high thermal shock resistance, and an excellent chemical resistance.

Furthermore, the glass preferably has a glass diameter of 25X 10 ^-7 ～80×10 ^-7 Wire thermal expansion at/DEG CCoefficient of expansion (CTE).

The compressive stress of the glass container is preferably 300MPa or more, more preferably 350MPa or more. The compressive stress of the glass container is preferably 900MPa or less.

The thickness (wall thickness) of the glass container is preferably 50 μm or more, more preferably 100 μm or more. The thickness of the glass container is preferably 2mm or less, more preferably 1mm or less. Since the present container has the F layer, high impact resistance can be exhibited even in a glass container having a relatively thin thickness.

Alkali-containing aluminosilicate glasses generally contain Na ₂ O and/or K ₂ O and SiO ₂ And Al ₂ O ₃ It may also contain at least one alkaline earth metal oxide and at least one alkali metal oxide as optional components.

The alkali-containing aluminosilicate glass is preferably free of boron and boron-containing compounds.

The alkali-containing aluminosilicate glass may contain a trace amount of a metal selected from SnO ₂ 、ZrO ₂ 、ZnO、TiO ₂ And As ₂ O ₃ Is present in the metal oxide layer. These ingredients are added as clarifying agents and/or chemical durability enhancing agents.

SnO may be formed on the outer surface of the glass container ₂ 、ZrO ₂ 、ZnO、TiO ₂ 、As ₂ O ₃ Etc.

Specific examples of borosilicate glass include Corning (registered trademark) Pyrex 7740, 7800, wheaton 180, 200, 400, schottky Duran, schottky Fiolax, KIMAX (registered trademark) N-51A, gerescheimer GX-51Flint, and the like.

Specific examples of the soda lime glass include Wheaton 800 and 900. As the soda lime glass, a soda lime glass treated with ammonium sulfate can be used.

The method for producing a glass reinforced container according to the present invention (hereinafter also referred to as "the present method") is a method in which a liquid composition containing particles of an F polymer (hereinafter also referred to as "F particles") is applied to the outer surface of a glass container and heated, and an F layer having a thickness of more than 1 μm containing the F polymer is formed on the outer surface of the glass container, thereby obtaining the present container.

For the above reasons, the present container obtained is excellent in impact resistance, heat resistance and UV resistance.

In the present method, the liquid composition is preferably applied directly to the outer surface of the glass container. In other words, in the present method, it is preferable that the liquid composition is applied to the outer side surface of the glass container and heated to directly form the F layer on the outer side surface of the glass container. In this case, the impact resistance, heat resistance and UV resistance of the present container thus obtained tend to be further improved for the reasons described above.

In the liquid composition, the D50 of the F particles is preferably 10 μm or less, more preferably 5 μm or less. The D50 of the F particles is preferably 0.1 μm or more, more preferably 1 μm or more. F particles having D50 in this range tend to have good fluidity and dispersibility.

Further, the specific surface area of the F particles is preferably 1 to 25m ² Preferably 1 to 8m ² /g。

The F particles may further contain a resin or an inorganic substance other than the F polymer, but preferably contain the F polymer as a main component. The content of the F polymer in the F particles is preferably 80 mass% or more, more preferably 100 mass%.

Examples of the resin include heat-resistant resins such as aromatic polyesters, polyamideimides, (thermoplastic) polyimides, polyphenylene oxides, polyphenylene ethers, and maleimides. Examples of the inorganic filler include silicon oxide (silica), metal oxide (beryllium oxide, cerium oxide, aluminum oxide, basic aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (steatite). At least a part of the surface of the inorganic filler may be surface-treated with a silane coupling agent (3-aminopropyl triethoxysilane, vinyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-isocyanatopropyl triethoxysilane, etc.).

The F particles containing a resin or an inorganic substance other than the F polymer may have a core-shell structure having the F polymer as a core and the above-described component on the core, or may have a core-shell structure having the F polymer as a shell and the above-described component in the shell. The F particles are obtained by, for example, combining (collision, agglomeration, etc.) particles of the F polymer with particles of the above-described component.

The liquid composition may contain an inorganic filler in addition to the F particles. If the liquid composition contains an inorganic filler, an F layer excellent in low linear expansion property is easily formed.

As the inorganic filler, silicon oxide (silica), metal oxide (beryllium oxide, cerium oxide, aluminum oxide, basic aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, magnesium metasilicate (steatite) are preferable.

The D50 of the inorganic filler is preferably 0.01 to 20. Mu.m.

The shape of the inorganic filler may be any of a granular shape, a needle shape (fibrous shape), and a plate shape. Specific examples of the inorganic filler include spheres, flakes, layers, leaves, almonds, pillars, cockscombs, equiaxed, leaves, micas, blocks, plates, wedges, rosettes, meshes, and prisms.

When the liquid composition contains an inorganic filler, the amount thereof is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, relative to the entire liquid composition.

From the viewpoint of improving the adhesiveness and low linear expansibility of the F layer, the liquid composition may further contain a resin material other than F particles (F polymer).

The resin material may be either thermosetting or thermoplastic. The resin material may be modified.

Examples of the resin material include tetrafluoroethylene polymers other than F polymers, aromatic polyimides, aromatic polyamic acids as aromatic polyimide precursors, aromatic maleimides, acrylic resins, phenolic resins, liquid crystalline polyesters, liquid crystalline polyester amides, polyolefin resins, modified polyphenylene ethers, polyfunctional cyanate resins, polyfunctional maleimide-cyanate resins, polyfunctional maleimides, aromatic elastomers such as styrene elastomers, vinyl ester resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea polycondensation resins, polycarbonates, polyarylates, polysulfones, polyarylsulfones, aromatic polyamides, aromatic polyether amides, polyphenylene sulfides, polyaryletherketones, polyamide imides, polyphenylene ethers, and epoxy resins.

The tetrafluoroethylene polymer other than the F polymer is preferably PTFE as described above. When the liquid composition contains PTFE particles, the D50 is preferably 0.1 to 6 μm. When the liquid composition contains PTFE particles, the amount thereof is preferably 10 to 50% by mass relative to the entire liquid composition.

When the liquid composition contains a resin material other than PTFE, the amount thereof is preferably 40 mass% or less relative to the entire liquid composition.

The liquid composition may contain other components such as a thixotropic agent, a viscosity modifier, an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weather-resistant agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, an electrically conductive agent, a mold release agent, a surface treatment agent, and a flame retardant, in addition to the above components.

The liquid composition preferably contains a liquid dispersion medium. The liquid dispersion medium is a liquid having a function of dispersing or dissolving the components constituting the liquid composition, and is a liquid compound inert at 25 ℃.

The liquid dispersion medium may be water or a nonaqueous liquid dispersion medium.

The liquid dispersion medium is preferably a liquid compound selected from the group consisting of water, amides, ketones and esters, more preferably water, N-methyl-2-pyrrolidone, γ -butyrolactone, methyl ethyl ketone, cyclohexanone and cyclopentanone, from the viewpoint of improving the dispersion stability of each component in the liquid composition.

In this case, it is preferable that the liquid dispersion medium of different types is compatible with each other.

The boiling point of the liquid dispersion medium is preferably 125 to 250 ℃. When the amount is within this range, the F particles flow highly and are densely packed when the liquid dispersion medium is removed from the liquid composition, and as a result, a dense F layer is easily formed.

The content of the liquid dispersion medium in the liquid composition is preferably 40 to 80% by mass, more preferably 50 to 70% by mass.

The liquid composition may contain a nonionic surfactant in view of improving dispersion stability and handleability.

Specific examples of the surfactant include "Ftergent" series (made by Seisaku corporation), "Surflon" series (made by AGC's chemical company, surflon is a registered trademark), "MEGA FACE" series (made by DIC corporation, MEGA FACE is a registered trademark), and "Unidyne" series (made by Dain Kogyn corporation, BYK-349), unidyne is a registered trademark), and "BYK-347", "BYK-349", "BYK-3450", "K-3451", "BYK-3455" (made by BYK-3456) (made by Pick chemical company, KF's chemical company, and "BYK-6043" BYK's chemical company, BYK-3451).

The viscosity of the liquid composition is preferably 10 mPas or more, more preferably 20 mPas or more. The viscosity of the liquid composition is preferably 1000 mPas or less, more preferably 500 mPas or less, and even more preferably 100 mPas or less.

The thixotropic ratio of the liquid composition is preferably 1.0 or more. The thixotropic ratio of the liquid composition is preferably 3.0 or less, more preferably 2.0 or less.

In this case, the liquid composition having the above characteristics is excellent in coatability (particularly, coatability by dip coating) and uniformity, and a denser F layer is easily formed.

Examples of the method of applying the liquid composition to the outer surface of the glass container include dip coating, spray coating (spray coating using a spray gun), roll coating, spin coating, gravure coating, microgravure coating, gravure offset coating, doctor blading, touch coating, bar coating, die coating, meyer bar coating, and slit die coating, and dip coating is particularly preferred. The formation of the F layer on the outer side surface of the glass container is more facilitated by dip coating.

The liquid composition applied to the outer surface of the glass container is preferably heated to remove the liquid dispersion medium (dried) to obtain a dried film, and then the dried film (F polymer) is further heated to be fired to form the F layer.

The heating temperature for removing the liquid dispersion medium is preferably 0 to 150 ℃ lower than the boiling point of the liquid dispersion medium. For example, in the case of using N-methyl-2-pyrrolidone (NMP) having a boiling point of about 200 ℃, the heating temperature is preferably 150℃or less, more preferably 100 to 120 ℃.

In addition, the liquid dispersion medium may be removed by air-drying.

After the liquid dispersion medium is removed, the F polymer is preferably heated at a firing temperature, more preferably at a temperature of 300 to 400 ℃.

The step of applying and drying the liquid composition to the layer F may be performed only once or two or more times. For example, the liquid composition may be applied and dried to obtain a dried film, the liquid composition is further applied and dried on the dried film to obtain a thick dried film, and then the dried film (F polymer) is fired by heating to form the F layer.

The method for producing a drug container of the present invention is a method for producing a drug container in which a sterilized container is obtained by exposing the container to an atmosphere (high-temperature atmosphere) or ultraviolet light at a temperature of 200 ℃ or higher and a temperature of not higher than the melting temperature of an F polymer, and the container is filled with a drug and sealed, thereby obtaining a drug container in which the drug is contained in the container.

The specific temperature of the high temperature atmosphere is preferably 250 to 300 ℃.

The time for exposing the container to the high temperature atmosphere is preferably 0.5 to 12 hours, more preferably 1 to 6 hours.

The wavelength of the ultraviolet light to be irradiated is preferably 240 to 290nm.

The cumulative irradiation amount of ultraviolet rays is preferably 1 to 200mJ/cm ² 。

Examples of the pharmaceutical product contained in the present container include a chemical substance itself which can be used for diagnosis, treatment, disposal or prevention of a disease, a composition containing at least one such chemical substance, and the like. The form of the pharmaceutical product may be any form such as a liquid, a solid, a gel, a suspension, an emulsion, or a powder.

The glass reinforced container, the method for producing the pharmaceutical container, and the method for producing the glass reinforced container according to the present invention have been described above, but the present invention is not limited to the configuration of the above embodiment.

For example, the glass reinforced container of the present invention may be added to the structure of the above embodiment, or may be replaced with any structure that performs the same function.

The method for producing a pharmaceutical container and the method for producing a glass reinforced container according to the present invention may be replaced by any process that performs the same function, in addition to the above-described embodiments.

Examples

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

1. Details of the ingredients

[ particle ]

F particle 1: from a mixture containing 97.9 mol% TFE units, 0.1 mol% NAH units and 2.0 mol% PPVE units, per 1X 10 ⁶ Particles (D50: 2.1 μm) composed of 1000 carbonyl group-containing polymers having a main chain of carbon atoms (melting temperature: 300 ℃ C., compressive strength: 15 MPa)

F particle 2: particles (D50: 2.3 μm) composed of a polymer (melting temperature: 255 ℃ C., compressive strength: 10 MPa) containing 75 mol% of TFE units and 25 mol% of hexafluoropropylene-based units with respect to the whole units

[ glass Container ]

Glass container 1: small bottle composed of borosilicate glass (thickness: 2 mm)

2. Preparation example of liquid composition

Powder composed of F particles 1, a nonionic silicone surfactant (product name: BYK-3450, manufactured by BYK Co.), a pH buffer, and water were put into a pot, and zirconia balls were put into the pot. Then, the pot was rolled at 150rpm for 1 hour to obtain a liquid composition 1 (viscosity: 30 mPas, pH: 8 to 9) containing F particles 1 (40 parts by mass), a silicone surfactant (2 parts by mass), a pH buffer (2 parts by mass) and water (56 parts by mass).

Liquid composition 2 (viscosity: 20 mPas, pH: 9) was obtained in the same manner as in liquid composition 1 except that the powder composed of F particles 1 was replaced with the powder composed of F particles 2.

Further, an aqueous dispersion of PTFE (trade name AD-915E, manufactured by AGC Co., ltd.) which is a commercially available product and contains 60 mass% of non-heat-fusible PTFE particles (D50: 0.3 μm) was used as the liquid composition 3.

Further, a powder composed of F particles 1, a silicone surfactant, and a liquid composition 3 were mixed to obtain a liquid composition 4 (viscosity: 50 mPas). The pH of the liquid composition 4 was adjusted to 10 by adding an appropriate amount of aqueous ammonia.

3. Example of production of reinforced glass Container

A liquid coating film is formed on the outer surface of the glass container by dip coating in which the glass container 1 is immersed in the liquid composition 1. Then, the glass container 1 having the liquid coating film formed thereon was passed through a drying furnace at 120 ℃ for 5 minutes, and dried by heating, to obtain a dried coating film.

Thereafter, the dried film was heated in a nitrogen oven at 380 ℃ for 3 minutes. Thus, a glass reinforced container 1 having a glass container 1 and an F layer (thickness: 25 μm) of a fused firing product containing F particles 1 on the outer surface thereof was obtained.

Glass-made reinforcing containers 2 to 4 were obtained in the same manner as the glass-made reinforcing container 1, except that the liquid compositions 2 to 4 were used in place of the liquid composition 1, respectively.

The transmittance of each F layer of the glass reinforced containers 1 to 4 at a wavelength of 255 to 355nm is 80% or more.

The glass container 1 was immersed in a solution containing 0.1 mass% of aminopropyl silsesquioxane, and a liquid coating was formed on the outer surface thereof. Then, the glass container 1 having the liquid coating film formed thereon was heated in a convection oven at 100 ℃ for 15 minutes to form a base layer.

Subsequently, the glass container 1 having the base layer is immersed in the liquid composition 3 to form a liquid coating film on the base layer. Then, the glass container 1 having the liquid coating film formed thereon was passed through a drying furnace at 120 ℃ for 5 minutes, and dried by heating, to obtain a dried coating film.

Then, the dried film was heated in a nitrogen oven at 380 ℃ for 3 minutes. Thereby, an F layer (thickness: 25 μm) of a fused firing product containing F particles 1 was formed, and a glass-made reinforced container 5 comprising a glass container 1 and a base layer and an F layer in this order on the outer surface thereof was obtained.

4. Evaluation

4-1. Adhesion

A long slit was cut into the F layer of each of the glass reinforced containers 1 to 5, and the maximum load at 90℃peeling from one end of the long strip in the longitudinal direction was evaluated as peel strength (N/cm) by a tensile tester at a tensile speed of 50mm/min, according to the following criteria.

[ evaluation criteria ]

O: the peel strength is 8N/cm or more.

Delta: the peel strength is 5N/cm or more and less than 8N/cm.

X: the peel strength is less than 5N/cm.

4-2. Heat resistance

After heating the glass reinforced containers 1 to 5 in an oven at 260℃for 1 hour, the appearance of the F layer was visually observed and evaluated according to the following criteria. The glass reinforced container 3 was not evaluated because of insufficient adhesion of the F layer.

[ evaluation criteria ]

O: the whole of the F layer is tightly adhered to the glass container 1.

X: the F layer was peeled from the glass container 1.

UV resistance

After irradiating the glass reinforced containers 1 to 5 with ultraviolet light having a wavelength of 270nm for 1 hour, the appearance of the F layer was visually observed and evaluated according to the following criteria. The glass reinforced container 3 was not evaluated because of insufficient adhesion of the F layer.

[ evaluation criteria ]

O: the F layer is not degraded and the surface is smooth.

X: the F layer deteriorates and the surface is not smooth.

The above evaluation results are summarized in table 1 below.

TABLE 1

The glass reinforced container 1 has the highest transparency and the highest internal recognition of the F layer formed on the surface of the container. The F layer formed on the container surface has the lowest friction, less foreign matter adhesion, and excellent transportation property, and is a glass reinforced container 4.

Industrial applicability

The glass reinforced container of the present invention is excellent in impact resistance, heat resistance and UV resistance, and therefore can be used as a container for storing pharmaceuticals and the like, which is required to be highly hygienic.

The entire contents of the specification, claims and abstract of japanese patent application No. 2021-002416 to which application is filed on 1-8 of 2021 are incorporated herein by reference as the disclosure of the specification of the present invention.

Claims

1. A glass reinforced container comprising a glass container and a polymer layer having a thickness of more than 1 [ mu ] m provided on the outer surface of the glass container, wherein the polymer layer comprises a tetrafluoroethylene polymer having a carbonyl group or hydroxyl group and having a melting temperature of more than 260 ℃.

2. The glass reinforced container according to claim 1, wherein the tetrafluoroethylene polymer has a compressive strength exceeding 12MPa.

3. The glass reinforced container according to claim 1 or 2, wherein the tetrafluoroethylene polymer is 1X 10 ⁶ Tetrafluoroethylene polymer with 10-5000 main chain carbon numbers and containing carbonyl groupsAnd (3) a compound.

4. The glass reinforced container according to any one of claims 1 to 3, wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer containing a perfluoro (alkyl vinyl ether) -based unit.

5. The glass reinforced container according to any one of claims 1 to 4, wherein the glass container is made of borosilicate glass or alkali-containing aluminosilicate glass.

6. The glass reinforced container according to any one of claims 1 to 5, wherein the glass container has a thickness of 2mm or less.

7. The glass reinforced container of any of claims 1 to 6, wherein the polymer layer further comprises polytetrafluoroethylene.

8. The glass reinforced container of any of claims 1 to 7, wherein the polymer layer has a thickness exceeding 20 μιη.

9. The glass reinforced container of any of claims 1 to 8, wherein the polymer layer has a thickness of less than 40 μιη.

10. The glass reinforced container of any of claims 1-9, wherein the glass container is a vial, ampoule, bottle, or cartridge.

11. The glass reinforced container according to any one of claims 1 to 10, which is used in a pharmaceutical.

12. A method for producing a pharmaceutical product container, wherein the glass-made reinforced container according to any one of claims 1 to 11 is exposed to ultraviolet light or an atmosphere having a temperature of 200 ℃ or higher and a temperature of not higher than the melting temperature of the tetrafluoroethylene polymer, whereby the glass-made reinforced container is obtained after the sterilization treatment, and the glass-made reinforced container is filled with a pharmaceutical product and sealed, whereby a pharmaceutical product container in which the pharmaceutical product is contained in the glass-made reinforced container is obtained.

13. A method for producing a glass reinforced container, wherein a liquid composition comprising particles of a tetrafluoroethylene polymer having a carbonyl group or a hydroxyl group and having a melting temperature of more than 260 ℃ is applied to an outer surface of a glass container and heated, and a polymer layer having a thickness of more than 1 [ mu ] m comprising the tetrafluoroethylene polymer is formed on the outer surface of the glass container, thereby obtaining a glass reinforced container comprising the glass container and the polymer layer provided on the outer surface of the glass container.

14. The manufacturing method according to claim 13, wherein the liquid composition is applied to the outer side surface of the glass container by a dip coating method.

15. The method according to claim 13 or 14, wherein the viscosity of the liquid composition is 1000 mPa-s or less.